Cold-curable mixtures of cycloaliphatic polyepoxides and curing agents



United States Patent Otfice 3,379,653 Patented Apr. 23, 1968 3,379,653 COLD-CURABLE MIXTURES 0F CYCLOALI- PHATIC PQLYEPOXIDES AND CURING AGENTS Otto Ernst, Pfeflingen, Basel, and Hans Lehmann, Basel,

Switzerland, assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland No Drawing. Filed Oct. 6, 1964, Ser. No. 402,012 Claims priority, application Switzerland, Oct. 18, 1963, 12,793/ 63 10 Claims. (Cl. 260-2) ABSTRACT ()F THE DISCLOSURE Cold-curing compositions comprising It is known that cycloaliphatic polyepoxy compounds can be hot-cured with the aid of polycarboxylic acid anhydrides to form infusible and insoluble resins having good mechanical properties and particularly high heat distortion points. Cold-curing of cycloaliphatic polyepoxides, on the other hand, has hitherto been diificult. When one of the usual cold curing agents for epoxy resins is used, for example ethylenediamine, diethylenetriamine or tri ethylenetetramine, cycloaliphatic polyepoxides do not as a rule yield cured products having useful technical properties. Accordingly, it has already been proposed to coldcure cycloaliphatic polyepoxy esters, for example 6- methyl-3 ,4-epoxycyclohexyl-carboxylic acid 6-methyl-3,4- epoxycyclohexyl)methylester with a combined curing system consisting of maleic anhydride and a boron trifiuoride-amine complex. However, this curing reaction is very exothermic and consequently difficult to control so that strong local overheating and charring of cured mouldings and castings are observed when large batches are manufactured. It is another disadvantage of these known resin curing agent systems that the two ingredients of the curing system must be marketed separately since a mixture of maleic anhydride and the boron trifiuoride-amine complex is not storable. Therefore, the resin curing agent system must be offered to the consumer in the form of a three-component system.

It has now been found that the disadvantages mentioned above can be prevented by using for the cold-curing of cycloaliphatic polyepoxides a metal fluoborate in conjunction with a complex of boron trifiuoride with water, ammonia or an organic compound capable of forming complexes with boron trifiuoride. The exothermic heat released during the curing reaction is of a lesser order than that released in the known cold-curing with maleic anhydride and boron trifiuoride-amine complexes so that the curing reaction is easy to control and even with large batches light-colored castings and mouldings are obtained; the latter have in addition better mechanical properties and higher heat distortion points than the products obtained by the known cold-curing of cycloaliphatic polyepoxy esters. Furthermore, the metal fiuoborates are readily compatible with the boron trifluoride complexes so that the curing component can be offered in the market as a storable mixture. Thus the resin curing agent system can be offered to the consumer as a two-component system, which constitutes a considerable simplification compared with the known three-component systems.

Accordingly, the present invention provides cold-curing mixtures suitable for the production of coatings, castings, mouldings, adhesives and as interlayer material for laminates, characterized in that the said mixtures contain (a) a cycloaliphatic polyepoxy compound containing at least one 1,2-epoxy group in a five-membered or sixmembered ring,

(b) a metal fluoborate and (c) a complex of boron trifluoride and water, ammonia or an organic compound capable of forming complexes with boron trifiuoride, preferably a boron trifiuorideamine complex.

As cycloaliphatic polyepoxy compounds containing at least one six-membered ring carrying a 1,2-epoxide group, there may be mentioned:

limonenedioxide,

vinylcyclohexenedioxide,

cyclohexadienedioxide,

bis 3,4-epoxycyclohexyl) dimethylmethane;

epoxycyclohexylmethyl ethers of glycols or hydroxyalkyleneglycols such as diethyleneglycol-bis 3,4-epoxy-6-methylcyclohexylmehtyl ether;

ethyleneglycol-bis 3 ,4-epoxycyclohexylmethyl ether,

1,4-butanediol-bis( 3',4'-epoxycyclohexylmethyl) ether,

(3 ,4-ep oxycyclohexylmethyl -glycidylether;

(3 ,4-epoxycyclohexyl -glycidyl ether,

ethyleneglycol-bis(3,4-epoxycyc1ohexyl-ether,

1,4-butanediol-bis 3 ,4'-epoxycyclohexyl ether,

p-hydroxyphenyldimethylmethane-bis 3,4-epoxycyclohexyl ether;

bis 3,4-ep oxycyclohexyl ether;

(3',4-epoxycyclohexylmethyl) -3 ,4-epoxycyclohexylether;

3,4-epoXycyclohexane-1,1-dimethanol-diglycidylether.

epoxycyclohexane-1,2-dicarboximide, such as N,N-ethylenediamine-bis (4,5 -e poxycyclohexanel ,2-dicarb oximide) epoxycyclohexylmethy-l-carbamates, such as bis( 3,4-epoxycyclohexylmethyl)-1,3-toluylene-dicarbamate;

epoxycyclohexane-carboxylates of aliphatic polyols such 3-methyl-l,5-pentanediol-bis(3,4-epoxycyclohexanecarboxylate) 1,5 -pentanediol-bis 3 ,4-e poxycyclohexane-carboxyl ate) ethylene glycol-bis 3,4-epoxycyclohexane-carb oxylate 2,2-diethyl-l,3-propanediol-bis(3,4-epoxy-cyclohexanecarb oxylate),

1,6-hexanediol-bis 3,4-epoxycyclohexane-carboxylate Z-butenel ,4-diol-bis 3,4-epoxycyclohexane-carboxylate Z-butene-1,4-diol-bis(3,4-epoXy-6-methy1cyclohexanecarboxylate),

1, l l -trimethylol pro pane-tris- 3,4-epoxy-cyclohexanecarboxylate),

1,2,3-propanetriol-tris(3,4-epoxy-cyclohexanecarboxylate) epoxycyclohexanecarboxylates of hydroxyalkylene glycols such as diethylene-glycol-bis(3,4-epoxy-6-methylcyclohexanecarboxylate),

triethyleneglycol-bis-(3,4-epoxycyclohexanecarboxylate) epoxycyclohexylalkyldicarboxylic acid esters such as BF .2H O

boron trifluoride-ammonia complex; complexes of boron trifiuoride with ketones, diazonium salts, sulfides such as thiophene, Z-methylthiophene, carboxylic acids such as acetic acid; propionic acid, benzoic acid; carboxylic acid anhydrides such as acetic anhydride; carboxylic acid esters such as diethyloxalate; alcohols such as ethanol, 2,5-hexanediol, ethyleneglycol, 2-ethyl-1,3-hexanediol, 1,2-propyleneglycol, 2-methy1-2,4-pent-anediol,

1,3-butyleneglycol,

ether alcohols such as diethylene-glycols, triethyleneglycol,

ethyleneglycol monomethyl ether, 2,2.-dihydroxy-di-n-propy1 ether;

ethers such as dimethyl ether, diethyl ether, methylethyl ether, dibutyl ether, diamyl ether, isopropylbutyl ether,

cyclic ethers such as methylamyl ether, methylhexyl ether, eithyleneglycol dimethyl ether, phenylmethyl ether, benzylethyl ether,

dibenzyl ether;

furan,

tet-rahydrofuran,

tetrahydrofurfuryl alcohol, Z-methyltetrahydrofuran,

2,5 -dimethyltetra'hydrofuran,

bis (tetrahydrofurfuryl) phthalate, bis (tetr-afurfuryl) -maleate,

bis (tetra'hydrofurfuryl fonmal, dihydropyran,

tetrahyd-ropyran;

phenols such as phenol,

resorcinol,

pyrocatechol,

'bis (parahydroxyphenyl) dime thylmethane, 2,2-bis para-hydroxyphenyl) butane;

carboxylic acid amides such as acetamide, ethylv-aleramide, dimethylformamide, benzamide; propionamide, benz-oguanamine, dimethylpropionamide, urea; valeramide,

preferred use is made of complexes of boron trifluoride with amines for example primary, secondary or tertiary amines such as stearylamine,

aminoethylethanolamine;

cycloalkylamines such as 6 cyclohexylamine, dicyclohexylamine;

araliphatic amines such as benzylarnine,

dimethylbenzylamine;

tris (dimethylaminomethyl -phenol;

aromatic amines such as aniline,

methylaniline,

di-me'thylaniline,

ethylaniline,

butylaniline,

phenylhydrazine,

benzylaniline,

ortho-, metaand para-phenylenediamine,

ortho-, metaand para-toluidine,

diphenylamine,

triphenylamine,

benzidine,

bis para-alminophenyl methane,

bis (para-aminophenyl sulfone;

Schiffs bases from aromatic amines, such as aniline, and aldehydes such as benzaldehyde; heterocyclic amines such hexamethylenetetramine, morpholine,

piperidine, pyridine,

pyridine homologues such as a-picoline, p-picoline and -picoline, 'lutidines such as 2,6 -lu tidine, collidines,

4-propanolpyri-dine, 2-vinylpyridine,

Z-ethanolpyridine, quinoline, 4-ethanolpy'ridine, isoquinoline, 2-hexylpyridine, quinaldine, Z-propanolpyridine, lepidi-ne,

aminopyridines such as Z-aminopyridine, 2-amino-4-methylpyridine or 2-amino-3 methylpyridine.

It may be of further advantage to use instead of a unitary boron trifiuoride complex a mixture of the complexes mentioned above or a mixed complex of boron trifiuoride with two or more of the afore-mentioned substances capable of forming complexes.

Particularly good results are obtained, for example, by using a combination of boron trifluoride-amine complexes, such as boron trifluoridemonoethylamine complex, with complexes from boron trifluoride and cyclic ethers, such as BF -bis(tetrahydrofurfuryl)phthalate complex.

The boron tn'fiuorlde complex is advantageously used in an amount of 0.1 to 20%, preferably 1 to 15%, by weight, referred to the amount of cycloaliphatic polyepoxy compound used.

The invention further provides a process for curing cycloaliphatic polyepoxy compounds containing at least one 1,2-epoxide group attached to a five-membered or sixmembered ring, preferably at room temperature, wherein there is used as curing agent a metal fluoborate together with a complex of boron trifiuoride and water or ammonia or an organic compound capable of forming complexes with boron trifluoride, preferably a boron trifluoride-amine complex.

The term curing as used in this context describes the polymerization of the polyepoxy compound to yield insoluble and infusible resins having good mechanical pro crties. In certain cases curing may consist in simply mixing the epoxy compound with the curing system at room temperature or a moderately higher temperature. In certain cases curing may alternatively be per-formed at an elevated temperature, for example ranging from 50 to C.

According to the curing process of the invention there is first prepared a curable two-component system, the component (1) consisting of the cycloaliphatic polyepoxy compound, whereas component (2) is a stable, storable mixture of a metal fluoborate with the boron trifiuoride complex. Such a two-component system may be marketed as a commercial product of practically unlimited storability at the ordinary room temperature, which may be converted by the consumer into the ready casting resin, laminating resin, coating medium, adhesive or plastic foam by simply mixing or melting the two components together.

The curable mixtures of the cycloaliphatic polyepoxy compound, the curing agent and the accelerator, or the curable two-component systems may be admixed at any phase prior 'to curing with an active diluent, filler, plasticiser, pigment, dyestuff, flame-inhibitor or mould lubricant.

As active diluents there may be used, for example, lowviscose monoepoxides such as butylglycide, butanediol diglycidyl ethers, 4-oxatetracyclo(6.2.l )hendecan-9-ol or 4--(3',4'-epoxycyclohexyl)-3,5-dioxacyclohexanol.

Suitable extenders and fillers are, for example, rutil, mica, quartz powder, rock meal, alumina trihydrate, calcium carbonate, ground dolomite, gypsum or barium sulfate.

To improve the mechanical properties there may be fur- 3 pared from 1 g. of boron trifluoride dihydrate and 49 g. of his tetrahydrofurfuryl phthalate);

In experiments 7 and 8 100 g. each of epoxy resin A are mixed with 10 g. of BF -monoethyl-amine complex, and with 5 and 10 g. respectively of BF -bis(tetrahydrofurfuryl) phthalate complex;

In experiments 9 to 12 100 g. each of epoxy resin A are mixed with 10 g. each of aqueous Zinc fluoborate solution (800 g./liter) and 10, 5, 2 and 0.5 g. respectively of BF -bis(tetrahydrofurfuryl)phthalate complex;

In experiments 13 to 17 100 g. each of epoxy resin A are mixed with the amounts shown in the following Table of aqueous zinc fluoborate solution, BF -monoethybamine complex and boron fluoride-bis(tetrahydrofurfuryl)phthalate complex.

All mixtures being prepared at room temperature. The mixture is then poured in each case into aluminum tubes (140 x x 10 mm.) and cured for 14 hours at room temperature.

The following Table 1 lists the mechanical properties and the heat distortion points of the resulting castings.

The heat distortion points according to Martens (DIN) of the specimens of this invention are substantially superior to those of comparative specimens, provided the latter can be cured at all or are at all applicable owing to their excessive reactivity.

TABLE 1 Experiment 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Epoxy resin A 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Zinc fluoborate 1 7 10 15 10 10 1 10 5 6 8. 5 5. 7 5 B Fg-monoethylaminc complex 1 0 10 10 5 6 1. 75 1. 15 1 BFt-bis(tetrahydrofurfuryDphthalate complex 2 10 5 10 10 6 2 0. 5 5 3 1. 1.15 0 Heat distortion point accdg. to Martens (DIN) Floxural strength, kgJrnm Impact strength, cmkg./cm Remarks 1 Aqueous solution containing 800 g./liter.

Prepared from 1 part of boron fluoride (BFufiHsO) and +19 parts of bis(tetraliydrofurfuryl)phthalate.

= Casting brittle.

ther incorporated fibers or fabrics of glass, polyesters, nylon, polyacrylonitrile, silk or cotton.

For the manufacture of foamed plastics there may be further added the usual propellants, for example compounds that give off carbon dioxide or nitrogen under the curing conditions, and/or low-boiling inert organic liquids, such as trichlorofluoromethane.

The curable mixtures of this invention may be used without or with fillers, if desired in the form of solutions or emulsions, as laminating resins, paints, lacquers, dipping resins, casting resins, coating compositions, pore fillers, putties, adhesives, moulding compositions, plastic foams, insulating compounds for the electrical industry and for the manufacture of such products.

Percentages in the following examples are by weight.

Example 1 In experiments 1 to 3 g. each of 3-(3,4-epoxycycl0hexy)9,l0 epoxy 2,4 dioxaspiro(5.5)undecane (epoxy resin A), containing 6.3 epoxide equivalents per kg, are mixed with 7, 10 and 15 g. of aqueous zinc fiuoborate solution (800 g./liter);

In experiment 4 100 g. of epoxy resin A are mixed with 10 g. of boron trifluoride-monoethylamine complex (marketed under the trademark BI- 100);

In experiments 5 and 6 100 g. of epoxy resin A are mixed with 10 g. and 50 g. respectively of boron tritluoride bis(tetrahydrofurfuryl)phthalate complex (pre- 4 No curing occurs.

5 Mixture too reactive, gells on mixing.

6 Casting brittle, not completely cured.

7 Mixture too reactive, casting decomposes.

Example 2 In experiment 1 100 g. of 6-methyl-3,4-epoxycyclohexylcarboxylic acid (6-methyl 3,4 epoxycyclohexyl) methyl ester, marketed under the trade name Unox 201 (epoxy resin B), containing 6.56 epoxide equivalents per kg, are mixed with 11 g. of maleic anhydride and a solution of 0.7 g. of BF -monoethylamine complex in 7 g. of ethyleneglycol.

In experiment 2 100 g. of epoxy resin B are mixed with 10 g. of an aqueous zinc fluoborate solution (800 g./ liter).

And in experiment 3 100 g. of epoxy resin B are mixed with a solution of 2 g. of BF -monoethylamine complex in 10 g. of an aqueous zinc fluoborate solution (800 g./ liter) all mixtures being prepared at room temperature and then cured for 14 hours at room temperature.

The following Table 2 lists the mechanical properties and the heat distortion points of the resulting castings.

Compared with experiments 1 and 2 the mixture used in experiment 3 displays a better heat distortion behaviour. Another striking feature is the lighter color of the castings by virtue of the better controllability of the exothermic curing reaction. Whereas the mixture of maleic anhydride with the BF -amine complex is not storable, the mixture of the BF -amine complex with the zinc fluoborate solution displays a good shelf-life. The curable system of experiment 1 must therefore be marketed as a three-component system, whereas the curable system of experiment 3 can be marketed as a two-component system.

TABLE 2 Experiment l Blackish (exothermic reaction). 2 Light brown.

Example 3 In experiments 1 and 2 80 g. and 70 g. respectively of epoxy resin A (cf. Example 1) and 20 g. and 30 g. respectively of (4-oxatetracyclo)-6.2.1.O .0 (hendec 9- 1 Example 4 In experiments 1 to 3 100 g. each of epoxy resin A (cf. Example 1);

In experiment 4 80 g. of epoxy resin A and 20 g. of active diluent C (cf. Example 3); and

In experiments and =6 80 g. each of epoxy resin A and 20 g. of active diluent D (of. Example 3) were mixed with the amounts, shown in the following Table 4, of copper fluoborate solution (45% aqueous solution) and BF -monoethylamine complex at room temperature, poured into aluminum tubes (140 x 40 x mm.) and cured at room temperature as described in Example 2.

The following Table 4 lists the heat distortion points of the resulting castings. As will be seen, these casting resins of the invention display heat distortion points according to Martens (DIN) that are extremely high for articles cured at room temperature.

yl) glycidyl ether (epoxy resin C), containing 6.8 epoxide equivalents per kg.;

TABLE 4 Experiment 1 2 3 4 5 6 Epoxy resin A, g 100 100 100 80 80 80 Active diluent C g Active diluent D, g 20 20 Copper fluoborate, 45% aqueous solution, g 2 1. 8 1. 4 1. 4 1. 8 1. 4

Eli -monoethylamine complex, g. 5 4. 2 5. 6 5. 6 4. 2 5. 6 Heat distortion point accdg. to Martens (DIN), C. 154 163 180 149 127 133 Example 5 In experiments 3 and 4 80 g. each of epoxy resin A and 20 g. of 3-vinyl-9,10 epoxy 2,4-dioxaspiro(5,5)- undecane (active diluent D) containing 4.8 epoxide equivalents per kg.;

In experiments 5 and 6 100 g. of epoxy resin A and 20 g. of butanediol diglycidyl ether (active diluent -E), containing 7.8 epoxide equivalents per kg. were mixed with the amounts shown in the following Table 3 of aqueous zinc fiuoborate solution (800 g./liter), BF monoethylamine complex and boron fluoridebis(tetrahydrofurfuryD-phthalate complex [prepared from 1 part of boron fluoride dihydrate and 49 parts of bis(tetrahydrofurfuryD-phthalate], at room temperature and then cured as described in Example 2.

The following Table 3 lists the properties of the curable mixtures as well as the mechanical properties and heat distortion points of the cured castings.

In experiments 1 to 3 100 g. each of epoxy resin A (cf. Example 1) were mixed with 2 g. each of boron trifluoride-monoethylamine complex [marketed under the tradename BF 400] and with 2 g. each of boron trifluoridebis (tetrahydrofurfuryl)phthalate complex [prepared from 1 g. of boron trifluoride dihydrate and 49g. of bis- (tetrahydrofurfuryl)phthalate] and with 12 g. of 10% cadmium fiuoborate solution in tetrahydrofurfuryl alcohol, 10 g. of 25% strontium fluoborate solution in tetrahydrofurfuryl alcohol or 10 g. of 40% barium fiuoborate solution in tetrahydrofurfuryl alcohol, then poured into aluminum tubes (140 x 40 x 10 mm.) and cured for 14 hours at room temperature.

The following Table 5 lists the mechanical properties and heat distortion points of the cured castings.

TABLE 3 Experiment 1 2 3 4 5 6 Epoxy resin A 80 80 100 Epoxy resin 0 20 30 Active diluent D 20 20 Active diluent E 20 20 Zinc fluoborate solution (800 g./liter of water). 5. 7 5. 7 8. 5 5. 7 6 5. 7 IBM-monoethylamine complex 1. 15 1. 15 1. 75 1. 15 6 1. 15 BFs-bis(tetrahydrofurturyl)phthalate complex 1.15 1.15 1. 75 1.15 3 l. 15 Viscosity of resin curing agent mixture at 25 0.,

in centipoises 7500 4000 4000 5000 850 1300 Shelf-life at 25 C. (viscosity rising to 10.000 centipoises), in minutes 10 30 25 20 60 50 Heat distortion point acedg. to Martens (DIN),

G 138 103 112 94 102 Flexural strength, in kgJmrn. 4 5 5 4 11 7 Impact strength, in emkgJem. 2 1 2 1. 5 4 4 1 Prepared from 1 part of BFa-ZHzO and 49 parts of bis(tetrahydrofuriuryl)phthalate.

TABLE 5 Experiment 1 2 3 Example 6 In experiment 1 100 g. of epoxy resin A were mixed with 10 g. of a solution of nickel fiuoborate in tetrahydrofurfuryl alcohol (containing 190 g. of nickel fiuoborate per liter) and 0.1 g. of boron trifluoride dihydrate.

In experiments 2 and 3 100 g. each of epoxy resin A were mixed with 10 g. each of aqueous zinc fluoborate solution (800 g./liter) and 0.1 g. and 0.2 g. respectively of boron trifluoride-ethyletherate, then poured into aluminum tubes (140 x 40 x 10 mm.) and cured at room temperature for 14 hours.

The following Table 6 lists the mechanical properties and heat distortion points of the cured castings.

What is claimed is:

1. A cold-curable composition of matter comprising (a) a cycloaliphatic polyepoxy compound containing at least one 1,2-epoxide group attached to a carbocyclic ring with at least 5 and at the most 6 members,

(b) a metal fiuoborate, wherein the metal is of the group consisting of lithium, iron, cobalt, nickel, chromium, manganese, cadmium, mercury, beryllium, magnesium, calcium, strontium, barium, aluminium, vanadium, antimony, tantalum, lanthanum, tin, lead, copper and zinc, and

(c) a complex of boron trifluoride with a member selected from the group consisting of water, ammonia and organic compounds capable of forming a complex with boron trifiuoride.

2. A curable mixture as claimed in claim 1, containing as boron trifluoride complex (c) a boron trifluorideamine complex.

3. A curable mixture as claimed in claim 2, containing as boron trifiuoride complex (c) the boron trifiuoridemonoethylamine complex.

4. A curable mixture as claimed in claim 1, containing as component (0) a mixture of a boron trifiuoride-aniine complex and a complex of boron trifluoride with a cyclic ether.

5. A curable mixture as claimed in claim 4, containing as component (c) a mixture of the boron trifiuoride monoethylamine complex and the boron trifluoride-bis- (tetrahydrofurfuryl)phthalate complex.

6. A curable mixture as claimed in claim 1, containing the boron trifiuoride complex (0) in an amount of 0.1 to 20% by weight, referred to the weight of the cycloaliphatic polyepoxy compound (a).

7. A curable mixture as claimed in claim 1, containing as metal fluoborate (b) a member selected from the group consisting of zinc fluoborate, nickel fiuoborate, copper fluoborate, cadmium fluoborate, strontium fluoborate and barium fluoborate.

8. A curable mixture as claimed in claim 1, containing the metal iluoborate (b) in the form of the hydrate.

9. A curable mixture as claimed in claim 1, containing the metal fluoborate (b) in the form of a concentrated aqueous solution.

10. A curable mixture as claimed in claim 1, containing the metal fiuoborate (b) in an amount of 0.1 to 20% referred to the weight of the cycloaliphatic polyepoxy compound (a).

References Cited UNITED STATES PATENTS 3,004,952 10/1961 Brueschweiler et al. 26047 3,112,294 11/1963 Newey.

WILLIAM H. SHORT, Primary Examiner.

T. PERTILLA, Assistant Examiner. 

